Polyhedral borane diisocyanate polymers



United States Patent 3,383,357 POLYHEDRAL BORANE DIISOCYANATE POLYMERSJohn C. Sauer, Wilmington, Del., assignor to E. I. du

Pont de Nemours and Company, Wilmington, Del., a

corporation of Delaware No Drawing. Filed June 25, 1963, Ser. No.290,891

9 Claims. (Cl. 260-47) This invention relates to novel boron-containingpolymers and their preparation. Specifically, the invention concernspolycarboxamides in which the amide nitrogens in the repeating unit aretwo nitrogens each bonded directly to boron atoms of divalently anionicB and B boron cage recurring units, and their preparation.

The many uses of synthetic polymers underscore their importance in thechemical art and have stimulated the search for polymers with new orimproved properties. Recently two closely related, new chemicalentities, the polyhedral borane anions B H and B I-I together with theirsubstitution products, have been reported [Knoth et al., J. Am. Chem.Soc., 84, 1056 (1962)]. These anions and their substitution derivativescomprise a polyboron cage structure and are sometimes referred to as Bor B boron cages or as polyboron compounds. Polymers containing thesedecahydrodecaborate(2-) and dodecahydrododecaborate(2-) boron cages havenow been prepared from diisocy-anate substituted B or B polyboroncompounds.

The polymers of the invention may be described as polycarboxamideshaving the novel recurring units of the formula (1) li i llCNHB,,,Hm-n-2Xn-NHG where M is a cation, v is the valence of M, and 2/ vexpresses the number of M groups present in terms of the ratio of Mgroups to one B H X group;

X is halogen, hydrocarbyl (.Q), hydrocarbyloxy (-OQ),hydrocarbyloxyhydrocarbyloxy (-OQ'OQ), hydrocarbylcar-bonyl (-COQ), orhydrocarbylthio (SQ), all free of aliphatic unsaturation;

m is 10 or 12, and

n is a cardinal number between 0 and m2, inclusive; and when n isgreater than 1, the X groups can be the same or different.

In the foregoing description the Qs represent hydrocarbyl and Qrepresents divalent hydrocarbyl. Preferably X groups containinghydrocar'oyl radicals are those containing up to 12 carbon atoms.

The polymers may be prepared by reacting at least one diisocyanate ofthe formula 0 o NB Hm Xn-N o o with at least one complementarydifun-ctional reactant of the type well known to form polymers withdiisocyanates, as exemplified, for example, in U.S. 2,292,443; U.S.2,511,544; U.S. 2,268,586; and U.S. 2,284,637.

Thus the polycanboxamides may be alternatively defined by the formula itM it where M, v, X, m and n are as defined above and A is defined as amoiety supplied by a complementary difunctional reactant of the classknown to react with diisocyana-tes to form polymers.

The M and M components The group M in Formulas 1 and 3 may be any of awide number of cations. It may be, for example, an inorganic cation, oran organic or organo-inorganic cation.

When the valence of M is greater than 2, the term 2/v becomesfractional. In such cases, it is understood the term 2/v is used forconvenience only, and that there are actually no fractional numbers ofcations present. Therefore any amount of polymer containing a repeatingunit of Formula 1 or 3 contains a whole number of cations. The sameconsiderations apply to the term M' of Formula 2.

M or M can be a cation of any metal in the Periodic Table shown inDemings General Chemistry, fifth edition, page 156 (Wiley, 1944), i.e.,a metal of Groups I-A, II-A, III-A, lV-A, V-A, VI-A, I-B, II-B, III- B,IVB, VB, VIB, VII B, or VIII. For example, M can be lithium, potassium,rubidium, cesium, beryllium, magnesium, calcium, barium, strontium,copper, mercury, aluminum, tin, bismuth, silver, zinc, vanadium,chromium, manganese, ruthenium, cobalt, nickel, or any other metal.Preferred metal cations are those having valences of 1, 2, or 3.Especially preferred metals, for reasons of availability, are those ofGroups I-A and II-A, i.e., alkali metals and alkaline-earth metals.

M or M can also be an organic or organo-inorganic cation, for example,an ammonium, phosphonium, or sulfonium cation of the formula U U'NH UUN+, U P+, or U S+, where U is aliphatically saturated hydrocarbylbonded to the nitrogen, phosphorus, or sulfur through aliphatic carbon,U is aliphatically saturated hydrocarbyl, and two U and/or U groups canbe joined together, directly or through an oxygen heteroatom, to form analkylene or oxygen-interrupted alkylene radical. (Alkylene as used hererefers to a divalent, saturated, aliphatic hydrocarbon radical, e.g.,ethylene, -CH CH Because of easier availability, cations in which U andU' contain at most 12 carbons each and any alkylene group contains atmost 12 carbons are preferred. Examples are triisopro pl amm onium, Nmethyl-piperidinium, N-hexylmorpholinium,

pyridinium,

trihexylammonium,

diethyl- [2- fi-naphthyl) ethyl] ammonium, N,N- dipropylanilinium,

b enzyltrimethylammonium, tetraisopentylammonium,

didode cyldiethylammonium,

bu tyldimethyl (phenyl) ammonium,

1 1-dimethylhexamethyleniminium, tetrabenzylph osphonium,ethyltriphenylphosphoniurn, tetramethylphosphonium,isobutylethylmethylpropylpho sphonium,ethylpentamethylene-p-tolylphosphonium, tetr-a( a-naphthyl) phosphonium,triphenylsulfonium, methyltetramethylenesulfonium,benzyldodecylmethylsulfonium, methyldipentylsulfonium, andtrimethylsulfoniu-m.

An especially preferred group of cations of this type are those in whichthe U and/or U groups are the same and are lower alkyl, particularly thetetra(lower alkyl)ammonium cations.

A polymer having repeating units of Formula 1 or 3 and containing any ofthe above-recited cations can be made directly from a reactant ofFormula 2. Therefore, the M' in Formula 2 can be any of the cationsrecited above. However, the polymers of the invention are not limited tothose whose definition of M corresponds to that set forth above, for thepolymers whose cation M is obtained directly from the reactant ofFormula 2 can be subjected to a cation exchange reaction in which thecation is replaced by other cations of the type described below. Thisexchange is facilitated by the solubility of the polymers of theinvention in ionizing solvents such as dimethylfor-mamide,dimethylacetamide, and N-met'hylpyrrolidone. Any of the well-knowntechniques of cation exchange may be employed, particularly thoseinvolving the use of cation-exchange resins. Cations that can beintroduced by these techniques include, for example, cations of the typerecited above and also any of an extremely wide variety of other cationsdescribed below.

For example, by virtue of this possibility of cationexchange, M inFormula 1 or 3 can be hydrogen, arnmonium, or hydrazonium. As is thecase with monomeric compounds containing the B H and B H ions and theirsubstituted derivatives, when polymers of this invention in which M ishydrogen are prepared or worked with in the presence of electron-donorsolvents or diluents, the polymers are ordinarily isolated as solvates,in which the solvated molecules are presumably associated with thehydrogen ions. Typical donor molecules of this type, i.e., moleculesthat can associate with hydrogen ions, are water, alcohols, ethers,nitriles, and carboxamides. An average of more or less than one suchsolvate molecule can be associated with a given hydrogen ion. When M ishydrogen, the presence or absence of solvate molecules, and the degreeof solvation when such molecules are present, is not critical and is ofno particular importance to the present invention. It is to beunderstood, therefore, that the term hydrogen, as used here, i.e., as avalue of M, includes hydrogen ions solvated with molecules of the typesdiscussed above. This usage of the term hydrogen is based onnomenclature approved by the International Union of Pure and AppliedChemistry; see J. Am. Chem. Soc., 82, 5529-30 (1960 M can also, forexample, be a complex cation of any of the metals referred to above,e.g.,

tetramminecopper (II) di-amminezinc (II) diaquotetramminechromium (III)tris( 1 ,Z-propanediamine chromium (III) nitratopentamminecobalt(III)dichlorobisethylene diarninecobalt (III) dicyclopentadienyliron (III)dibenzenechromium (I) and tris acetylacetonato) silicon.

As a further example, M can also be any of a very broad class ofsubstituted ammonium or hydrazonium cations represented by the formulasU'Nl-l UU'NH U'N2H41L, UI2N2H3+, U 3N2Hg and UU3N2H+, Where U and U areas previously defined. Examples are rnethylammonium,cyclopropylammonium, l-methylheptylammonium,

2-( l-naphthyl ethylam-rnonium, diisobutylammonium,dicyclohexylammonium, dinonylammonium, morpholinium,dodecamethyleniminium, phenylhydrazonium,

l-methyll-phenylhydrazonium, l-methyl-2-isopropylhydrazonium,dodecylhydr-azonium, 1,1,2-triethylhydrazonium, and1,1,1-tritetrabenzylhydrazonium.

Because of availability, the preferred types of cations of thosedescribed in the preceding three paragraphs are hydrogen, ammonium,(lower alkyl)ammonium, and di- (lower alkyl)ammonium.

The X component Among the previously defined X substituents that containhydrocarbon moieties, a preferred class, for reasons of availability, isthat in which the Qs are alkyl or cycloalkyl of at most 12 carbon atoms,i.e., alkyl, alkoxy, alkoxyalkoxy, alkylcarbonyl, alkylthio, cycloalkyl,cycloalkyloxy, etc. An especially preferred class is that in which anyhydrocarbon moiety is saturated acyclic lower aliphatic hydrocarbon,i.e., lower alkyl. In this instance, each alkyl of the precedingsentence is preceded by the term lower.

Examples of X substituents include fluorine, chlorine, bromine, iodine,ethyl, tert-butyl, cyclohexyl, octyl, dodecyl, l-pheny-lethyl, methoxy,isopropoxy, cyclopentyloxy, phenoxy, 2-(2-naphthyl)ethoxy,Z-methoxyethoxy, -butoxyhexyloxy, 3-(p-tolyloxy)propoxy, ethylthio,isobutylthio, benzylthio, dodecylthio, acetyl, propionyl, isobutyryl,2-octanoyl, benzoyl, cycloheptanecarbonyl, pivaloyl, l-naphthoyl, andp-phenylbenzoyl.

Because of ease of preparation of intermediates, polymers in which therepeating unit of Formula 1 or 3 contain at most two X substituentsother than halogens, and particularly those containing no substituentsother than halogen, are preferred. The most easily preparedhalogencontaining compounds are the relatively highly halogenated ones,i.e. those in which n is between m-7 and m2, inclusive, and thesecompounds constitute a more preferred type. In the B series, anespecially preferred class is that in which n is 7 or 8, i.e., -m3 orm-2. In either the B or B series, chlorine is the preferred halogenbecause of its relatively low cost and ease of preparation ofintermediates.

The A component This moiety of the polycarboxamide polymers is suppliedby the complementary difunctional reactant and is best defined bydescribing said reactant.

This reactant contains two functional groups selected from carboxyl,hydroxyl, thiol, primary amino and secondary amino. Preferably the twofunctional groups are the same, i.e., the preferred complementaryreactants are dicarboxylic acids, diols, dithiols, di(primary amines),and di(secondary amines). When a secondary amine is present, the secondcarbon group attached to the am ne is preferably a lower alkyl group.

Thus, a preferred embodiment of the complementary reactant has formulawhere Y and Y each may be carboxyl, hydroxyl, thiol, primary amino orsecondary amino, and R is defined further below. In the most preferredembodiment Y and Y consist of identical functional groups, i.e., Y' Y.

Examples of diamine complementary reactants include ethylenediamine,trimethylenediamine, octamethylenediamine, dodecamethylenediamine, N,N'dimethylhexamethylenediamine, cyclohexylene-l,4-diamine,o-phenylenediamine, p-phenylenediamine, benzidine, naphthylene-1,4-diamine, 7-,-r-diamino dibutyl oxide, and T,-r-diaminodihexylsulfide.

Examples of dicarboxylic acid reagents include succinic acid, malonicacid, oxalic acid, pimelic acid, suberic acid, decane 1,10 dicarboxylicacid, cyclohexane 1,4 dicarboxylic acid, phthalic acid, terephthalicacid, naphthalenel,3-dicarboxylic acid, andbiphenylylene-2,2-dicarboxylic acid.

Examples of diol and thiol reagents include di(fi-hydroxyethyl)ether,decamethylene glycol, hexamethylene glycol, resorcinol,cyclohexane-1,4-diol, 2,2-di(4-hydroxyphenyl) propane, and thecorresponding thiols.

mer by known techniques, Polymers containing such additives are includedin the products of the invention.

Preparation of intermediates The starting materials for the preparationof the B and B boron cage intermediates are compounds containing the B Hand B H anions. These compounds are prepared as follows:

B compounds Preparation of B H Ammonium decahydrodecaborate, (NHQ B Hcan be prepared in quantitative yield by the reaction of a decaborylbis(lower dialkyl sulfide), e.g., decaboryl bis (dimethyl sulfide), B H[(CH S] with liquid ammonia at a temperature between about -50 C. and C.The product is isolated simply by evaporating any excess, unreactedammonia. This process is described in detail in US. Patent 3,148,938 inthe name of Walter H. Knoth, Jr. The decaboryl bis(lower dialkylsulfide) is prepared by allowing decaborane, B H to react with a lowerdialkyl sulfide at a temperature of at least 0 C., and preferably atleast 25 C., until approximately one mole of hydrogen per mole ofdecaborane is evolved. This process is described in detail in U.S.Patent 3,154,561 in the name of Earl L. Muetterties.

The NH,+ cation may be exchanged by ion-exchange methods to preparecompounds wherein the cation is as previously defined. For example, asolution of in 30 ml. of water is passed through a 0.5" diameterchromatography column containing 80 ml. of a commercial acidic exchangeresin (Aimberlite IR 120-H, the acid form of a crosslinkedpolystyrenesulfonic acid).

The water efiiuent is clear, colorless and acidic. The column is rinsedwith more water until the efliuent is no longer acidic and the waterfractions are combined. Evaporation of the combined aqueous solutionsunder reduced pressure (1 mm. mercury) at a temperature of about 40 C.leaves a yellow viscous liquid which is H B H -(H O) The compound canalso be written as (H30)2B10H10'H20. is neutralized to yield [(CH N] B Hwith isopropylamine to yield a 7 3)2 10 10- By substituting other aminebases for liquid ammonia in the process for preparing (NHQ B H a widerange of substituted ammonium derivatives can be obtained, e.g.,trimethylamine yields [(CH NH] B H and isopropylamine yields [(CH CHNH BH Similarly, tertbutylamine yields [(CH CNH B H and butyl amine yields(C4H9NH3)2B10H10.

The replacement of one cation by another is detailed in assigneescopending application Ser. No. 237,392, filed November 13, 1962, in thename of Walter H. Knoth, Jr.

Preparation of B dicarboxylic acids (NH B H is first converted to thebisdiazonium compound B H (N by reaction With NaNO /HCl in aqueoussolution at C. or lower, followed by reduction of the intermediateproduct (which is not isolated) with zinc and hydrochloric acid. Thebisdiazonium compound is separated from the crude solid product byextraction with alcohol. This process is described in detail inassignees copending application Ser. No. 186,270, filed April 9, 1962,in the name of Walter H. Knoth, Jr. now abandoned.

B H (CO) can then be prepared by reacting with carbon monoxide at125-250 C. and 500-1,000 atmospheres. B H (CO) is the sole product.Halogen groups (X in Formulas 1 and 2) can be introduced into the Bdicarbonyls just described by reacting a dicarbonyl with the appropriatefree halogen in aqueous solution at 0-100" C. The halogenated carbonylsare obtained by evaporation of the solutions, which gives hydrates ofthe halogenated acids, followed by dehydration of the latter by heating.The foregoing products and processes are described in detail in US.3,166,378.

The B dicarboxylic acids are prepared by reacting B dicarbonyls withwater, as described in the preceding paragraph, or, preferably, with anequivalent amount of a hydroxide containing the cation M. The cation, M,so introduced can be replaced by any other cation that can be a value ofM by conventional exchange-reaction techniques, including the use ofion-exchange resins. These processes are described in 'U.S. Patent3,166,378, and in more detail in said application Ser. No. 237,392.

Preparation of B diisocyanates A solution consisting of 1.0 g. of B H-2CO in 20 ml. of acetonitrile is added dropwise and with stirring to aslurry of 0.9 g. of sodium azide in 10 ml. of acetonitrile. Thetemperature rises to 50 C. and 230 ml. of nitrogen gas is evolved over a1-hour period. The reaction mixture is filtered into an aqueous solutionof (CH NCl and the solid which precipitates is separated. It iscrystallized from Water to Obtain g. of The identity of the compound isconfirmed by its infrared absorption spectrum and by elemental analyses.

Analysis.Calcd for [(CH N] B H (NCO) B, 31.0; C, 34.5; H, 9.2; N, 16.1.Found: B, 31.0; C, 34.1; H, 9.2; N, 16.2.

The ultraviolet spectrum of the compound in acetonitrile shows thefollowing: Amax, 217 (e=22,800).

The M component may be exchanged for other Ms through ion-exchangemethods.

A solution, consisting of 4.0 g. of

in ml. of CH CN, is cooled to 5 C. and chlorine gas is passed throughfor 4.5 hours, maintaining the temperature at 5-l0 C. The solution,which is dark blue, is allowed to stand about 18 hours at atmospherictemperature and the blue color fades to yellow. The solvent is removedby evaporation to obtain a viscous liquid as the residue. The liquid isstirred with ethyl alcohol and a solid separates. The solid, which is[(CH N] B Cl (NCO) is removed and dried to obtain 5.6 g. of product.

Analysis.Cald fOI' [(CH3)4N]2B1 Cl3(NcO) B, 17.3; C, 19.2; H, 3.8; Cl,45.4; N, 9.0. Found: B, 16.6; C, 19.5, 19.7; H, 3.9, 4.2; CI, 46.0; N,9.0.

These procedures are detailed in said application Ser. No. 237,392.

Preparation of B diamines A mixture of B H -2N and liquid ammonia heatedat 200 C. in a sealed platnium tube at 1000 lbs. pressure will produce HB H (NH It can also be prepared by reacting B H -2CO, H NOSO H and NaOHat room temperature, or by refluxing [(CH N] B H (NCO) with 5% NaOH.

Again, ion-exchange methods enable one to alter the cationic componentof the product.

The chlorinated diisocyanates obtained above may be refluxed with water,ethyl alcohol and NaOH to obtain B chlorinated diamines.

These procedures are explained in said application Ser. No. 237,392.

Preparation of B dithiols B dithiols may be prepared by treating B H -2Nwith H 8 and heating at C. or more under autogenous pressure.Halogenated dithiols may be obtained by starting with the halogenated Ncompound.

These procedures are detailed in said application Ser. No. 237,392.

Preparation of B diols To obtain compounds containing the B H (OH) ion,(NH B H is reacted with N-methylpyrrolidone in the From the foregoing,the polymers of the invention may alternatively be described aspolycarboxamides having recurring units of the formula m m-n-2XnN HC Z p-Rq Z Where M, v, X, m and n are defined as previously; Z and Z are thesame or different and represent (oxy gen), S (sulfur) or where Y ishydrogen or lower alkyl; 2 is 0 (zero) or 1, q is 0 or 1, p being 0 whenq is 0; and R is (a) a divalent hydrocarbyl group free of aliphaticunsaturation which may be interrupted by 0, S or N atoms, or (b) adivalent group of the formula where M, v, m, n, and X" have the samedefinitions as M, v, m, n, and X as previously set forth.

When R is a divalent hydrocarbyl group, it may be further defined asdivalent, aliphatically saturated hydrocarbyl of from 2-12 carbons(e.g., alkylene, cycloalkylene, cycloalkylenedialkylene,alkylenebis(cycloalkylene), arylene, aralkylene, alkarylene,alkylenediarylene, or arylenedialkylene), in which any carbon chain canbe interrupted in a non-cyclic portion thereof by up to one or twoseparated oxygen, sulfur, or nitrogen hetero atoms, said hetero atomsbeing removed by at least one carbon and preferably two carbons from thefunctional groups bonded to R.

From Formula 5 it is evident that the term polycarboxamide defines apolymer having the recurring linkage Thus the term polycarboxamideincludes the terms polyurethan, polythiourethan and polyurea.

The process In the process of the reaction, equivalent quantities of thediisocyanate polyboron reactant and complementary difunctional reactantare ordinarily used. Nonequivalent quantities can be used if desired,but polymers of relatively low molecular weight result. Since thereaction mixtures may contain more than one of the polyborondiisocyanates and/ or difunctional reactants, the polymers of theinvention include copolycarboxamides formed from such mixtures.

In addition to the monomeric starting materials described above, therecan be present, as reactants, compounds that polymerize by ring-opening.The products of the invention therefore include copolymers containingrepeating units derived from these cyclic monomers. Examples of suchmonomers include the lactams, e.g., ecaprolactam, and r-butyrolactam.

The reaction mixture may also include as coreactants, organicdiisocyanates other than the polyboron diisocyanates. Such diisocyanatesinclude, for example, ethylene diisocyanate, butylene-1,3-diisocyanate,cyclohexylene-1,2-diisocyanate, phenylene diisocyanates, etc.

In addition to the foregoing described reactants and coreactants, smallamounts of monoisocyanates, monocarboxylic acids, mono(primary orsecondary) amines, mono alcohols or thiols can be added to control themolecular weights of the polymers produced.

Optionally, a catalyst of the type commonly employed for condensationreactions of isocyanates with carboxylic acids, amines, alcohols andthiols may be added to the polymerization mixture. However, such acatalyst is not necessary.

A solvent or diluent is not required for any of the processes, sincepolymerization even of reactants that are solids at ordinarytemperatures can be brought about by heating to high enoughtemperatures. To permit operation at lower temperatures, however, and insome cases to moderate the reaction between reactive starting materials,an inert solvent or diluent or mixture thereof is frequently used. Ingeneral, any liquid free of groups that react with isocyanates,carboxylic acids, primary amines, secondary amines, alcohols, and thiolsin the absence of a catalyst can be used. Examples are hydrocarbons(e.g., benzene, xylene, heptane, cyclohexane, and decahydronaphthalene);carboxylic acid amides free of hydrogen bonded to nitrogen (e.g.,N-methylpyrrolidone, dimethylformamide, and dipropylacetamide); nitriles(e.g., acetonitrile, butyronitrile, and benzonitrile); ethers (e.g.,butyl ether and 1,2-dimethoxyethane); and chlorinated hydrocarbons(e.g., chlorobenzene, chloroform, and ethylene chloride). Mixtures ofany of the above can be used.

The temperature can vary widely and will depend in part on the nature ofthe complementary difunctional reactant employed. For diamines, diolsand dithiols, the process may be carried out at temperatures between 50and 275 C., with to 225 C. being preferred. For dicarboxylic acidreactants, the temperature may range between 90 and 400 C., with ZOO-350C. being preferred.

Pressure is not a critical factor in the process, for the reaction maybe carried out at atmospheric, subatmospheric or superatmosphericpressures. The pressures used for most convenience are atmosphericpressure or the autogenous pressures of a closed system.

Time is not a critical factor of the process. It can vary widelydepending on the reactants, the solvent (if any), the temperature, andthe molecular weight desired, and can range from 1 hour to several days.The progress of the polymerization can be followed by taking out smallsamples of the reaction mixture, determining their infrared absorptionspectra, and observing to what extent absorptions characteristic of thereactants have disappeared and absorptions characteristic of the productare present.

The polymeric products can be isolated by evaporating any volatilematerials present or by drowning the reaction mixture in a non-solventand filtering, washing, and drying the product. Water, a lower alkanol,or an inert hydrocarbon such as heptane is usually suitable as anonsolvent.

The polymers of the invention are solids or viscous liquids and arestable to air and water.

The preferred polymers, particularly for use in preparing films, havemolecular weights above 10,000. However, polymers of lower molecularweight, e.g., in the 3,000-10,000 range, can be used in preparingcoatings.

The products of the invention are characterized by the fact that ontreatment with aqueous mineral acids, e.g., hydrochloric acid, they arehydrolyzed to give (a) the polyboron diamine corresponding to thepolyboron diisocyanate used to prepare the polymer, i.e.,

which can also be written as B H X (NH and (b) the complementarybifunctional reactant, or its mineral acid salt when said reactant is anamine. The formula of the complementary bifunctional reactant soproduced can be written as A-Z -R -Z' -A where p is O or 1, A is -COOHwhen p is 0 and A is --H when p is 1, and Z, R, Z and q are defined asin Formula 5.

Inert materials such as dyes, pigments, fillers, delusterants,plasticizers, and antioxidants can be incorporated in the polymers,either by being included in the polymerization mixtures or by beingmixed with the preformed polypresence of concentrated hydrochloric acidat 170 C. The compound 13 1-1 (N-methylpyrrolidone) thus produced isheated with sodium hydroxide to give the compound Na B H (-OH) Thesodium ion can be exchanged for other cations, e.g.,tetramethylammonium, by wellknown ion-exchange techniques referred toabove. Halogenated B diols are prepared by direct reaction of theappropriate halogen with an acidic aqueous solution of H B H (OH)obtained by simply acidifying at -100 C. For example, [(CH N] B Cl (OH)may be prepared by the following procedure.

A reaction vessel is charged with 60 g. of bis,N-methyl-2-pyrrolidone)octahydrodecaborane(8) and a solution of g. of sodiumhydroxide in 500 ml. of water. The mix ture is refluxed for one hour. Itis cooled and sufiicient hydrochloric acid is added to form a neutralsolution. Chlorine gas is bubbled into the solution and the solution isgradually heated to the boiling point over a period of one hour and tenminutes. Passage of chlorine is stopped and suflicient aqueous sodiumhydroxide is added to form a neutral solution. The reaction mixture isnow poured onto 50 g. of (CH NOH. The mixture is cooled and the solidproduct which is present is separated by filtration. It isrecrystallized from water containing a small amount of acetonitrile toobtain The infrared absorption spectrum of the product shows a smallband at 4.0 1. (B-H bond).

Analysis.Calcd for [(CH N] B HC1 (OH) C, 17.8; H, 5.0; N, 5.1; CI, 46.1.Found: C, 18.2; H, 5.1; N, 5.1; CI, 46.5.

These processes are also described in said application Ser. No. 237,392.

Preparation of B compounds containing X substituents The usual processesof halogenation, alkylation, and acylation may be employed. The halogensmay be used to introduce halo substituents, olefins to introduce alkylsubstituents, acyl halides for if C Q etc.

B compounds Preparation of B H The primary starting material for thepreparation of the B compounds is B H Any alkali-metal salt of the acidH B H can be prepared by the reaction of the appropriate alkali-metalhydroborate, e.g., NaBH with diborane in the presence of an ether suchas ethyl ether or 1,2-dimethoxyethane. The process is carried out in aclosed system at a temperature of at least 100 C. and at autogenouspressure, which pressure should be at least three atmospheres. Theproduct can be recrystallized from ethers such as ethyl ether ortetrahydrofuran or mixtures thereof. Any organic solvent ofcrystallization can be removed by mixing the product with water anddistilling out the organic solvent. The product is then isolated byevaporation. The sodium salt is thus obtained as a hydrate, the exactdegree of hydration depending on the extent of drying. Hydrates of theacid H B H can be prepared by simply acidifying the sodium salt with astrong mineral acid such as HCl or by bringing a solution of the sodiumsalt into contact with an acidic cation-exchange resin. The acidhydrates are isolated by evaporation, the degree of hydration obtainedagain depending on the extent of evaporation. These processes aredescribed in assignees copending application Ser. No. 38,099, filed May23, 1960, in the name of Henry C. Miller and Earl L. Muetterties nowabandoned.

The H cation may be exchanged by ion-exchange methods to preparecompounds containing a broad range of cations, as previously described.

Preparation of B dicarboxylic acids B H (CO) is first prepared byreacting a hydrate of H B H with carbon monoxide at 60-150 C. and500-1,000 atmospheres. This process is described in assignees copendingapplication Ser. No. 206,554, filed June 28, 1962, in the name of JohnC. Sauer.

Compounds containing the B H (COOH) anion are prepared by reacting thecorresponding dicarbonyl, B H (CO) with water or an aqueous hydroxidecontaining the cation M of Formula 5. The resulting compounds of theformula M B H (COOH) can be halogenated directly with the appropriatefree halogen in aqueous solution at temperatures of about 25150 C. Theexact temperature depends on the halogen to be introduced and the degreeof substitution desired. For example, treatment of Cs B H (COOH) withexcess chlorine at -100 C. in aqueous solution, followed by cationexchange with tetramethylammonium chloride, gives Esters, acid halides,and amides of these acids are made in the same manner as thecorresponding B acid derivatives. The foregoing processes are describedin Ser. No. 246,636, filed December 21, 1962, in the name of H. C.Miller and E. L. Muetterties.

Preparation of B diisocyanates A solution of B H -2CO in acetonitrile isadded with stirring to a solution of sodium azide in acetonitrile. Afternitrogen gas evolution has ceased, the reaction mixture is filtered andthe filtrate evaporated by a stream of air until a viscous syrupremains. The syrup is diluted with water and an aqueous solution of (CHNCl is added with stirring. A white precipitate forms which is separatedto obtain [(CH N] B H (NCO) The product may be recrystallized fromwater.

Chlorinated diisocyantes may be prepared by bubbling gaseous chlorinethrough an aqueous solution of B H -2CO. After chlorination is complete,the solution is evaporated to dryness in a sublimation unit and theresidue is sublimed to obtain a sublimate on the water cooled condenser.A portion of the sublimate is dissolved in dry CH CN and a suspension ofNaN in CH3CN added to the solution with stirring. The mixture is heatedto incipient reflux temperature for 1 hour and then evaporated todryness. The residue is dissolved in water and an aqueous solution of(CH NCl is added in excess. The precipitate which forms is separated andheated to boiling with 60 ml. of water. The solid dissolves partiallyand the hot mixture is filtered. The filtrate is chilled and a solidprecipitates. The compound, which is is separated, washed and dried.

Preparation of B diamines Na B H -2H 0 and H NOSO' H in 250 ml. of wateris neutralized by adding, at a temperature below 25 C. a solution ofsodium hydroxide in water. The solution is heated cautiously until anexothermic reaction begins and is then cooled to moderate the reactionwhich continues for about 30 minutes. The solution is now cooled toabout 5 C. and the precipitate which forms is separated to obtain 9 g.of H B H (NH as a white crystalline solid.

Preparation of B diols A solution consisting of Na B H -2H O andN-methyl- 2-pyrrolidone is stirred and hydrochloric acid is added. Themixture is filtered and the filtrate distilled until a pot temperatureof 205 C. is reached. The mixture is held at this temperature for 4hours and it is then poured into ethyl alcohol. The precipitate whichforms is separated by 1 1 filtration. It is purified by dissolving inacetonitrile and reprecipitating with ethanol. The product (7.8 g.) soobtained (which is is mixed with 50 ml. of 6% aqueous NaOH solution, themixture is refluxed for 4 hours and then allowed to cool.

A portion of the above reaction mixture is added with stirring to asolution of 6 g. of (CH NOH in 400 ml. of ethyl alcohol. The mixture isevaporated to dryness, leaving a syrupy residue. The residue is mixedwith 150 ml. of isopropyl alcohol and forms an oil. The oil iscrystallized from solution in aqueous ethyl alcohol to yield bis(tetramethylammonium) dihydroxydecahydrododecaborate (2).

Preparation of B dithiols A mixture consisting of hydrated crystallineand an excess of hydrogen sulfide is heated in a pressure vessel underautogenous pressure with agitation for 4 hours at 100 C. The vessel iscooled, vented and flushed with nitrogen. The reaction mixture isneutralized with cesium hydroxide and the precipitate which forms isseparated and recrystallized twice from water. The prodllCt isCS2B12H10(SH)2.

Preparation of B anions containing X groups The usual processes ofhalogenation, alkylation, and acylation may be employed. The halogensmay be used to introduce halo substituents, olefins to introduce alkylsubstituents; acyl halides, for

o H c-Q etc.

The following examples illustrate the products and processes of theinvention. For the sake of simplicity, the equations shown in thevarious examples are partly schematic in that they show only theformation of the repeating unit of Formula 3. It is understood that theactual product of each example is in fact a polymer containing therepeating unit shown.

EXAMPLE 1 A tubular glass reactor was charged with 2.500 g. of [(CH N] BH (NCO) 0.8329 g. of hexamethylenediamine, and 40 ml. of anhydrousacetonitrile. The reactor was then fiushed with nitrogen, sealed atatmospheric pressure, and heated at about 95 C. for eight days. Withinthe first twenty hours, an essentially complete solution formed, andwithin about three days, an extremely viscous product precipitated fromthis solution. The reactor was cooled and opened, and the viscousproduct was separated and dried thoroughly at 100 C./0.1 mm., to give atackfree, solid polyurea having the repeating unit shown in the aboveequation.

Analysis.-Calcd. for C H B N O C, 42.1; H, 8.8; N, 18.3. Found: C,41.5;H, 10.4; N, 18.5.

The inherent viscosity of an 0.25% solution of the polymer in water was0.88, whereas the inherent viscosity of an 0.25% solution of the polymerin aqueous 1% tetramethylammonium chloride was only 0.12. This viscositybehavior, which is typical of polyelectrolytes in aqueous solutions, wasevidence that a polymer had indeed been formed. The infrared absorptionspectrum of the polymer (mineral-oil mull) had absorption at 2.95 (amideNH), 3.29 4 (overtone of amide NH), 3.41 ,a and 3.49u

12 (saturated C-H), 4091.0 (B-H), 6.2 (broad) and 6.5 (amide @O).

A brilliantly clear film of the polymer was made at 190 C./1000 lb./sq.in. in a Carver press. Tough, hard, clear coatings that adhered well tosteel, aluminum, and glass were made on these substrates from aqueoussolutions of the polymer containing about 0.5% glycerol based on thepolymer, by flowing out a layer of the solution and evaporating thewater.

EXAMPLE 2 o It A reactor like that of Example 1 was charged with 0.9820g. of [(CH N] B H (NC0) and 0.5642 g. of 4,4'-di(aminophenyl) ether,flushed with nitrogen, and sealed at atmospheric pressure. The mixturewas heated at 225 C. for about five minutes, at 180 C. for four hours,and then at 195 C. for 18 hours. The product obtained after cooling andopening the reactor was a solid polyurea having the repeating unit shownin the above equation. It was soluble with difficulty indimethylacetamide, dimethylformamide, and dimethyl sulfoxide.

Analysis.-Calcd. for C H B N O N, 15.3. Found: N, 14.7.

The infrared absorption spectrum of the polymer (mineral-oil mull)showed bands at 3.0;/. and 3.1a (amide NH) and at 6.28;; and 6.65 (amideC 0).

A mixture of 0.6 g. of the polyurea and 20 ml. of concentratedhydrochloric acid was refluxed for four hours. Glacial acetic acid (20ml.) was added, and the mixture was refluxed for four hours more andevaporated to dryness. The solid residue was charged to a tubular glassreactor along with 8 ml. of constant-boiling hydrobromic acid. Thereactor was cooled to C., evacuated, sealed, heated at C. for 18 hours,cooled, and opened. The solid and liquid in the reactor were separatedby filtration. Infrared analysis showed that the dihydrobromide of4,4'-di(aminophenyl) ether was present in the solid. Evaporation of thefiltrate to dryness gave identified by comparison of its infraredabsorption spectrum with that of an authentic sample.

A reactor like that of Example 1 was charged with an intimate mixture of1.5823 g. of

and 0.5000 g. of hydroquinone, flushed with nitrogen, evacuated, sealed,and heated at 220-240 C. for three hours. During this time a viscousmelt was formed. The reactor was cooled and opened, and the solidproduct was washed with warm water and dried, to give a solidpolyurethan having the repeating unit shown in the above equation.

Analysis.-Calcd. for C H B N O C, 41.9; H, 8.3; N, 12.2. Found: C, 41.5;H, 8.6; N, 12.8.

The inherent viscosity of the polymer was 0.06 (0.25% solution indimethylformamide). The infrared absorption spectrum (mineral-oil mull)had absorption at 3.2,u (amide NH), 4.01.4 (8-H), and 6.3a (amide C=O).

[wt-min].

NHBmH -NHCO(CHz)aO A reactor like that of Example 1 was charged with0.5715 g. of [(CH N] B H (NCO) 0.2107 g. of 1,6- hexanediol, and 0.1 g.of anhydrous hydrogen chloride. The reactor was evacuated, sealed undervacuum, and heated at 125 C. for three hours. The reactor was cooled andopened, and the layer of solid that had formed on the walls of thereactor was separated from other material therein. This product was apolyurethan having the repeating units of the above equation, as shownby its infrared absorption (mineral-oil mull) at 3.0; (amide NH), 4.03,.(B-H), and 6.18; (amide C=O).

EXAMPLE 5 [(OHahNh O CN-BmHg-NCO HS--(CH2)4-SH f [(CHahNh -CNHBH5-NH-S(CH2)4S A reactor like that of Example 1 was charged with 2.5071 g. of[(CH N] B H (NCO) 0.8627 g. of 1,4- butanedithiol, and 10 ml. ofdimethylacetamide. The reactor was flushed with nitrogen and sealed atatmospheric pressure. It was heated at about 95 C. for six hours, atISO-107 C. for seven days, and at 225 C. for five days. A homogeneousmixture formed soon after the temperature was raised to 225 C. Thereactor was cooled and opened, and volatile material was evaporatedunder reduced pressure. The non-volatile product was a solidpolythiourethan having the repeating unit of the above equation. Theinfrared absorption spectrum of the product (mineral-oil mull) showedabsorption at 3.0 11 (amide NH), 4.0,u (strong; B-H), and 62,11.(strong) and 6.5, (weak) (amide C=O).

EXAMPLE 6 mNh NH-BinHa-NHC(OHg)g 00;) In an atmosphere of nitrogen, areactor like that of Example 1 was charged with 1.0900 g. of

0.6333 g. of sebacic acid, and 5 ml. of acetonitrile. The open end ofthe reactor was closed with a rubber cap fitted with a narrow-boregas-inlet tube (the lower end of which was free of the reaction mixture)and a similar gas-exit tube. A slow stream of nitrogen was passedthrough the reactor from the gas-inlet tube throughout the process.Thus, volatile material could be released slow- 1y from the reactorthrough the gas-exit tube, but only nitrogen could enter the reactor.The reactor was heated at 100 C. for about one hour, during which timemost of the acetonitrile volatilized. It was then heated at 200 C. for18 hours, at 280 for three hours, and at 340 C. for one hour. At thispoint a small sample of the reaction mixture showed infrared absorptioncorresponding to unreacted isocyanate groups. The mixture was thereforeheated at 340 C. for 24 hours more. A sample of the mixture now showedincreased carbonyl absorption and greatly reduced isocyanate absorption.The mixture was heated at 340 C. for 18 hours, the reactor was cooledand opened, and the solid product was washed with hot water and dried.There was thus obtained a polyamide having repeating units of the typeshown in the above equation. The infrared absorption spectrum of theproduct (mineral-oil mull) showed absorption at 3.1,u. (amide NH), 4.0;.(B-H), and 6.3 and 6.5, (amide C=O).

14 EXAMPLE 7 Copolyurea of [(CH N] B HCl (NCO) and 2,4- tolylenediisocyanate with 4,4-di(aminophenyl) ether A mixture of 0.1552 g. of[(CH N] B HCl (NCO) 0.8128 g. of 2,4-tolylene diisocyanate, 0.9795 g. of4,4- di(aminophenyl) ether, and 25 ml. of 1,2-dimethoxyethane wascharged to a reactor like that of Example 1. The reactor was sealed,evacuated, held at ordinary temperature (20-30 C.) for 2.5 days, andthen heated at C. for 24 hours. The reactor was cooled, and the reactionmixture was filtered. The infrared absorption spectrum of the solid thusobtained showed that some unreacted isocyanate groups were stillpresent. A mixture of the product, 0.10 g. of 4,4'-di(aminophenyl)ether, and 15 ml. of 1,2-dimethoxyethane was charged to a similarreactor. The reactor was evacuated, sealed, and heated at 125 C. forfour hours, after which it was cooled and opened, and the reactionmixture was drowned in water. The solid copolyurea that precipitated wasseparated by filtration and dried at C./ 0.1 mm. over P 0 The infraredabsorption spectrum of the copolyurea (mineraloil mull) had absorptionat 3.1 3 (N-H), 4.1,u (weak; B-H), and 6.1 3, 6.3;, and 6.4 (amide C=O).Absence of absorption 4.5,u. indicated that the isocyanate groups hadall reacted.

EXAMPLE 8 A reactor like that of Example 6 was charged with 0.7946 g. of[(CH N] B Cl (NCO) 0.1553 g. of 1,4- butanedithiol, and 20 ml. ofacetonitrile, and the resulting solution was heated at 60-90" C. for 2.5days in an atmosphere of nitrogen. At the end of this time the solidobtained by removing volatile material from a small sample of thepolymerization mixture still showed slight absorption in the infraredcorresponding to -NCO groups. 1,4-butanedithio1 (0.2 g.) was added tothe remainder of the mixture, and the reactor was sealed and heated at130 C. for 48 hours. It was then cooled and opened, and volatilematerial was evaporated to give a solid polythiourethan having therepeating unit of the product of the above equation.

Analysis.-Calcd. for C14H34B10C18N402S2: C, H, 4.6; S, 8.5. Found: C,20.5; H,4.9; S, 6.8.

The infrared absorption spectrum of the product indicated essentiallycomplete reaction of the diisocyanate.

EXAMPLE 9 A reactor like that of Example 1 was charged with g. Of [(cH)4N]2B12H o(NC/O)2, g. Of hfiX- amethylenediamine, and 20 m1. ofacetonitrile. The reactor was cooled to about 80 C., evacuated, sealed,and heated at 95 C. for 3.5 days. The reactor was cooled to roomtemperature and opened, volatile material was re moved from the productby evaporation, :and the residual solid was washed with water and dried,to give a solid polyurea having the repeating unit of the aboveequation.

AnalysiS.Calcd. for C16H50B12N602: C, H, N, 17.2. Found: C, 39.1; H,10.3; N, 16.8.

The inherent viscosity of the polymer (0.25% solution indimethylformamide) was 0.18.

In addition to the foregoing examples, the following table disclosespolyboron diisocyanates which can be reacted with the correspondingcomplementary reactant to obtain the desired polymer. The right handcolumn of the table indicates the general procedure by which theproducts may be prepared by referring to the appropriate detailedexample.

TABLE Polyboron Diiscyanato(s) Complementary Reactant(s) Prgledire 0PCHKMNhBwCIMNC h [(CzH5)aN l2B\0 a(CO0H)z 6 1L. (O4 9)4P]2Bl0C18(NCO)2NMBmCIflCOOH): 6 12.. [(CH3) S]zB Cl (NCO) Terephthalic acid 6 13.,CZIBrzHrolNCOh l,2-cyclohexanedicarboxylic no 6 14-- NazBmHflNCO);Di(4-carb0xybutyl) sulfide. 6 l5. KzBwB1' (NCO) Di(4-aminocyclohexylmethan 1 16 lvIgB H (OCLI (NCO)z m-Phenylenediamine 2 [(CHahNhBmHKCfiHU)k; 17 ins Di(3-am1nopropyl) ether 1 [(CH3)4 ]2 l0 G(C6 U)2( )2 18(C5H5NH) B;H CI (NCO):* Hcxamethylenediamine plus N,N-Dlrnethyl- 9hexarnethylenediamine. 19.. NfizB12H1u(NCO)z Nfi2B1zCl10(NH2)2 2 20 N aB1;I-I5F5(NC0) 'Iriethylene glycol... 4 2L- Li2B10Cl6(COCI'I3)2(NCO)Z1,10-decanediol 4 22.. [(O0I-I1;)4N]2B10H3I5(NCO);Di(6-hydr0xyhexyl)methylamin 4 23 BaBuH (SC5Hn)(NCO)z4-Di(2-hydroxyethyl)benzene. 4 24-... K2BmHsF2(NCO)2 KzBmHClflOH): 3 25[(CH3)-l l2 l0 8( C )2 [(C a): ]2B1oQ s(SH)z 5 26 RbzBmBr4Cl,-(NCO)g1,6-hcxanedithi0l 8 CH2CH2 CH3 27 /N B oCl7(OCHzCH2OCHa)(NCO);1,4-butanedithiol plus 1,10-decanedithiol 8 CH2CH2 C113 3 2S[(CGH5)3S12B1ZBT10(NCO)Z Dithiohydroqulnone 8 [(05115)sPCHalzBrzHMNCO):29 us 1,5 naphthalenedithiol 5 l( o s)aPC al2 w s( *CeHn is cyclohexyl;C5II NH is pyridinium.

The polymers of the invention form tough, clear films which adhere wellto steel, aluminum, glass, and other substrates as evidenced byExample 1. Thus, the polymers may be applied to the above-mentionedmaterials to form a hard, clear protective coating. In addition, thepolymers may be pressed into a clear, hard, self-supporting film asevidenced by Example 1. These self-supporting films may be used toreplace glass in instances where a clear substance is needed. The filmsare, thus, useful in many applications, for example, as lighttransparent neutron barriers and space vehicle windows resistant toouter space radiation.

As many apparently widely difierent embodiments of this invention may bemade without departing from the spirit and scope thereof, it is to beunderstood that this invention is not limited to the specificembodiments thereof except as defined in the appended claims.

The embodiments of the invention in which an exclusive property orprivilege is claimed are defined as follows:

1. A polycarboxamide consisting essentially of recurring units of theformula wherein M is a cation selected from the class consisting of ametal; U UNl-l U U'N+, U' P+, U S+, hydrogen, ammonium, hydrazonium, acomplex cation of a metal, UINH3+, UUNH UN H U N H U N H and UU' N I-Iwherein U is aliphatically saturated hydrocarbyl bonded to therespective N, P, and S atoms through aliphatic carbon; U' isaliphatically saturated hydrocarbyl, and any two U and U groups can bejoined to form a group selected from the class consisting of alkyleneand oxygeninterrupted alkylene which forms a ring with the N, P, and Satoms, v is the valence of M, Z/v is the ratio of M groups present toone B H X p;

X is selected from the class consisting of halogen,

hydrocarbyl, hydrocarbyloxy, hydrocarbyloxyhydrocarbyloxy,hydrocarbylcarbonyl, and hydrocarbylthio, wherein the hydrocarbyl groupsare free of aliphatic unsaturation and contain up to 12 carbon atoms;

in is a cardinal number selected from the class consisting of 10 and 12;

n is a cardinal number of from 0 to m2, inclusive,

and

A is a moiety derived from a difunctional reactant in which thefunctional groups are selected from COOH, -OH, -SH, NH and -NH (loweralkyl), said polycarboxamide having a molecular weight of at least 3000.

2. A polycarboxamide consisting essentially of recurring units of theformula M is a cation selected from the class consisting of a metal; UUNH+, U UN+, U' P+, U S+, hydrogen, ammonium, hydrazonium, a complexcation of a metal, U,NH3+, UU NH2 UN2H4 U 2N2H3' U N H and UU' N Hwherein U is aliphatically saturated hydrocarbyl bonded to therespective N, P, and S atoms through aliphatic carbon; U isaliphatically saturated hydrocarbyl, and any two U and U groups can bejoined to form a group selected from the class consisting of alkyleneand oxygcninterrupted alkylene which forms a ring with the N, P, and Satoms, v is the valence of M, 2/ v is the ratio of M groups present toone B H X p;

X is selected from the class consisting of halogen, hydrocarbyl,hydrocarbyloxy, hydrocarbyloxyhydrocarbyloxy, hydrocarbylcarbonyl, andhydrocarbylthio, wherein the hydrocarbyl groups are free of aliphaticunsaturation and are of at most 12 carbon atoms;

m is a cardinal number selected from the class consisting of 10 and 12;

n is a cardinal number of from 0 to m-2, inclusive;

Z and Z' are each selected from the class consisting of O, S, or

wherein Y is selected from the class consisting of hydrogen and loweralkyl;

p and q are each 0 or 1, inclusive, p being 0 when q is O; and

R is selected from the class consisting of (a) a divalent hydrocarbylgroup of 2 to 12 carbon atoms, inclusive, free of aliphaticunsaturation, which may be interrupted in a non-cyclic portion thereofby O, S, and N atoms; and (b) a divalent group of the formula where M",v, m", n", and X" have the same definitions as M, v, m, n, and X aspreviously set forth, said polycarboxamide having a molecular weight ofat least 3000.

3. The polymer of claim 2 in which X is halogen, Z and Z are the sameand R is the divalent hydrocarbyl group defined in part (a) of thedefinition of R in claim 3.

4. The polymer of claim 2 wherein p is zero.

5. A polycarboxamide consisting essentially of recurring units of theformula ii nor-ram]. --CNH-B10H5NH -NH(CH2)5NH said polycarboxamidehaving a molecular weight of at least 3000.

6. A polycarboxamide consisting essentially of recurring units of theformula said polycarboxamide having a molecular weight of at least 3000.

7. A polycarboxamide consisting essentially of recurring units of theformula i omL. -NH-Bwl1i H -'(C 2)usaid polycarboxamide having amolecular weight of at least 3000.

8. A polycarboxamide consisting essentially of recurring units of theformula i? [wanna]. -CNHBiaHs-NHC-(CHz)asaid polycarboxamide having amolecular weight of at least 3000.

9. A polycarboxamide consisting essentially of recurring units of theformula said polycarboxamide having a molecular weight of at least 3000.

18 References Cited UNITED STATES PATENTS 3,148,938 9/1964 Knoth 23-143,154,561 10/1964 Muetterties 260-327 3,166,378 1/1965 Knoth 23-143,093,687 6/1963 Clark et a1 260-606.5 3,167,590 1/1965 Heying 260606.53,258,479 6/ 1966 Alexander et al 260-485 3,270,047 8/1966 Heying et a1260-482 2,929,800 3/1960 Hill 260-77.5 2,888,438 5/1959 Manfred 260-4532,939,851 6/1960 Orchin 260-453 3,328,355 6/1967 Dawes et a1. 260-FOREIGN PATENTS 720,525 3/ 1966 Canada.

729,528 3/ 1966 Canada.

956,391 4/ 1964 Great Britain.

956,392 4/1964 Great Britain.

956,393 4/1964 Great Britain.

956,394 4/1964 Great Britain.

956,395 4/1964 Great Britain. 1,309,439 10/1960 France.

854,701 11/ 2 Germany. 1,089,974 9/ 1960 Germany.

956,256 4/1964 Great Britain.

OTHER REFERENCES Cram et al., Organic Chemistry, page 275, McGraw- Hill(N.Y.) (1959).

Fieser et al., Organic Chemistry, 2nd ed., page 647, Heath and Co.(Boston) (1950).

Royals, Advanced Organic Chemistry, page 618, Prentice Hall (EnglewoodCliffs), 1959.

Osborn, Synthetic Ion-Exchangers, The MacMillan Co. (1956) (pages 15-16cited as being of interest).

Journal of the American Chemical Society, vol. 84, Mar. 20, 1962, pages10561058 relied upon.

Chemical and Engineering News, May 9, 1966, pages 88-98 relied upon.

Olin Mathieson Chemical Corporation, Technical Report No. 4, QuarterlyProgress Report No. 2, report period Aug. 11, 1961 to Nov. 10, 1961, 5pages.

DONALD E. CZAJA, Primary Examiner.

LEON .T. BERCOVITZ, WALTER A. MODANCE,

Examiners.

F. MCKELVEY, H. I. MOATZ, Assistant Examiners.

1. A POLYCARBOXAMIDE CONSISTING ESSENTIALLY OF RECURRING UNITS OF THEFORMULA
 6. A POLYCARBOXAMIDE CONSISTING ESSENTIALLY OF RECURRING UNITSOF THE FORMULA